JPH0794610B2 - Monoazobenzothiazole compound and method for dyeing or printing hydrophobic fiber material using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a monoazobenzothiazole compound and a method for dyeing or printing a hydrophobic fiber material using the same.

(Prior Art) In recent years, along with the tendency for consumers to enhance their sense of leisure and strengthen their tendency to upscale, demand for textile products such as sportswear with deep and vivid colors is increasing. In particular, the development of a disperse dye capable of dyeing or printing polyester fibers in a deep and vivid color with good fastness is strongly desired.

Since sportswear and the like are frequently washed at home, there is a strong demand for wet fastness among fastnesses, and there is a particularly strong demand for dyes that cause less discoloration during home washing and less contamination of other fibers. However, conventional dyes have not always been satisfactory for the following reasons.
That is, as a recent trend, in order to increase the added value, various post-treatments such as softening, antistatic, and texture improvement are performed. Since these post-treatments are performed at high temperature, the dye bleeds and is washed. Robustness decreases. Further, in recent years, synthetic detergents mainly containing straight chain sodium alkylbenzene sulfonate have been mainly used in home laundry, but the action of synthetic detergents on dyed products is different from traditional soap, and generally other fibers, especially polyamide, There is more contamination on the acetate fibers. Therefore, it becomes a serious problem when polyamide fiber is used for patterning. Furthermore, JIS-L, which was a typical test method standard in Japan,
[0844] In the A-4 method, since Marcel soap was used as a detergent, the test results and the actual usage of consumers have become inconsistent. For this reason, JIS has been amended to add JIS-K3371 as a test method for home washing.
It was carried out on May 1, 1986, and in the same way, AATCC issued a revised bill in 1980 in the United States and ISO in 1982 in Europe. Old JIS A-4
The dyed products evaluated to have good fastness by the method do not always give good results under the test conditions corresponding to the domestic laundry represented by these.

The above discoloration during home washing and contamination of other fibers,
This is a particularly remarkable problem for red dyes. Because red type fibers are often used for deep color dyeing, not only is the color fading caused by the dye bleeding described above and stains on other fibers more likely to occur, but white spot stains are more prominent than other colors. This is because it is conspicuous.

Known as monoazobenzothiazole-based disperse dyes capable of dyeing hydrophobic fibers, especially polyester fibers in red, for example, JP-B-45-7712, JP-B-60-29784 and JP-A-57-109857. However, the compounds disclosed in these publications are desired to solve the above-mentioned problems.

(Problems to be Solved by the Invention) The present inventors have dyed or printed hydrophobic fibers, particularly polyester fibers, in red with excellent dyeability, and then used sunlight, sublimation,
As a result of diligent studies to find a compound that is excellent in various fastness properties such as water, and particularly can provide a dyed product having excellent fastness to washing,
The present invention has been completed.

(Means for Solving Problems) The present invention provides the following general formula (I). (In the formula, X represents a hydrogen atom, a chlorine atom or a methyl group, and R represents an alkyl group having 1 to 4 carbon atoms), and a hydrophobic fiber material is dyed with the monoazobenzothiazole compound. Alternatively, a method for printing is provided.

In the above general formula (I), X is a hydrogen atom, a chlorine atom or a methyl group, preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group. Examples of the alkyl group having 1 to 4 carbon atoms represented by R include methyl,
Ethyl, n-propyl, iso-propyl, n-butyl, i
So-butyl and the like are exemplified, but preferably a methyl group,
An ethyl group is preferable, and a methyl group is particularly preferable.

The compound represented by the general formula (I) can be produced, for example, by the following method. Formula (II) below 2-amino-4,6-dibromobenzothiazole represented by is dissolved or dispersed in a mineral acid such as hydrochloric acid, sulfuric acid or phosphoric acid, or an organic acid such as acetic acid or propionic acid, or a mixed solvent thereof, and when cold. It is preferably diazotized with sodium nitrite or nitrosyl sulfuric acid at 5 ° C. or lower. At that time, in some cases, the benzothiazole represented by the formula (II) is dispersed in the above-mentioned mineral acid, organic acid or a mixed solvent thereof and heated to preferably 70 to 100 ° C., and thereafter, up to the above temperature. It is expected that the reaction will proceed smoothly if it is cooled and diazotized. On the other hand, the following general formula (II
I) (In the formula, X and R have the above-mentioned meanings.), An aniline derivative represented by the following formula is used: a mineral acid such as hydrochloric acid or sulfuric acid; an organic acid such as acetic acid or propionic acid; or methanol, ethanol, dimethylformamide, tetrahydrofuran or the like. Is dissolved in the organic solvent or the mixed solvent thereof, and the diazonium compound is added thereto at a temperature of preferably 10 ° C. or lower in a cold state and coupling is performed. At that time, depending on the case, it is preferable to adjust the pH to 1 to 5 because the coupling occurs rapidly. After completion of the reaction, the precipitated crystals are separated to obtain the monoazobenzothiazole compound represented by the general formula (I).

The coupling component represented by the above general formula (III) has the following general formula (IV) (In the formula, X has the above-mentioned meaning.) N, N-
Di (hydroxyethyl) aniline derivative, toluene,
It is dissolved in an organic solvent such as pyridine, dimethylformamide, or tetrahydrofuran, and in the presence of a deoxidizing agent such as pyridine or triethylamine, the following general formula (V) ClCO ₂ R (V) (wherein R has the above meaning. ) It can be produced by reacting with a chlorocarbonic acid ester. At that time, it is particularly preferable to use pyridine as a solvent because it also acts as a deoxidizing agent.

Specific examples of the aniline derivative represented by the general formula (III) include the following.

N, N-di (methoxycarbonyloxyethyl) aniline N, N-di (methoxycarbonyloxyethyl) -m-toluidine N, N-di (methoxycarbonyloxyethyl) -m-chloroaniline N, N-di (ethoxy Carbonyloxyethyl) aniline N, N-di (ethoxycarbonyloxyethyl) -m-toluidine N, N-di (ethoxycarbonyloxyethyl) -m-chloroaniline N, N-di (n-propoxycarbonyloxyethyl) aniline N, N-di (n-propoxycarbonyloxyethyl)-
m-Toluidine N, N-di (iso-propoxycarbonyloxyethyl) aniline N, N-di (n-butoxycarbonyloxyethyl) aniline N, N-di (iso-butoxycarbonyloxyethyl) aniline N, N-di (Sec-Butoxycarbonyloxyethyl) aniline Further, as the compound represented by the general formula (I), the 2-aminobenzothiazole compound represented by the general formula (II) can be converted into N, N-di ( It can also be produced by coupling with a hydroxyethyl) aniline derivative and then reacting it with a chlorocarbonic acid ester represented by the general formula (V).

The monoazobenzothiazole compound represented by the general formula (I) of the present invention is useful as a disperse dye for hydrophobic fiber materials, particularly polyester fiber materials. For example, the compound of the present invention can be pulverized into fine particles in an aqueous medium together with a suitable dispersant, for example, a condensate of naphthalenesulfonic acid and formaldehyde or ligninsulfonic acid, to obtain a dye dispersion. The dye dispersion liquid can be used as it is or in the form of powder by spray drying or the like. The dyeing is performed by immersing the hydrophobic fiber material in an aqueous dyeing bath and pressing it at 105 ° C. or higher, preferably 110 to 140.
It can be performed at ° C. Further, dyeing is carried out in the presence of a carrier such as O-phenylphenol or trichlorobenzene at a relatively high temperature, for example, boiling water, or a dye dispersion is padded on a cloth and kept at 150 to 230 ° C. for 30 to 60 seconds. It is also possible to dye by so-called thermosol dyeing in which dry heat treatment is performed.

On the other hand, in the case of printing, the dye dispersion can be kneaded together with an appropriate sizing agent, padded on a cloth, and subjected to steaming or thermosol treatment for dyeing. A solvent dyeing method using an organic solvent such as trichlorethylene or perchlorethylene as a dyeing medium is also possible.

The resulting dyed product can be subjected to various post-treatments such as softening, water repellent, texture improving, antistatic, and sanitary as necessary, and various fastnesses even after the post-processing. In particular, it has the feature that the washing fastness does not decrease.

A dyed product obtained by dyeing or printing a hydrophobic fiber material, particularly a polyester fiber material, using the compound of the present invention represented by the general formula (I) has light fastness, sublimation fastness, wet fastness, etc. It has various fastnesses, and has the characteristic that the fastness to washing does not decrease even after heat setting or post-processing. For example, the fastness to washing when the polyester fiber material is dyed in a dark color (JIS 2/1 concentration) and then heat set is significantly superior to the existing red dye even under the above-mentioned test conditions corresponding to home washing.

In addition, the compound (I) of the present invention is excellent in dyeability, especially in dyeing strength and build-up property, so that a dark dyed product can be easily obtained. In the case of clothing such as the sportswear described above, since it is essential that dark-colored dyeing is desired and that laundry be washed frequently, excellent fastness to washing is indispensable. Therefore, the compound (I) of the present invention is used for such clothing. For dyeing
Especially excellent performance. Further, it may be used in combination with other dyes, and good results such as improvement of dyeability and modification of color tone can be expected.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the examples, parts are parts by weight.

Example 1 31 parts of 2-amino-4,6-dibromobenzothiazole was added to 85 parts.
% Disperse the phosphoric acid in 450 parts, raise the temperature to 90 ° C and
After keeping the temperature for a while, it was cooled, and 7 parts of sodium nitrite was gradually added while keeping it at 0 ° C. or lower to diazotize. On the other hand, N, N-di (methoxycarbonyloxyethyl) -m-toluidine
84 parts of a pyridine solution containing 31 parts was mixed with 350 parts of methanol, to which the diazonium compound was added while cooling to 5 ° C or lower. Then, 1200 parts of water was added, and the precipitated crystals were separated and dried to obtain the following formula (1) 54 parts of a monoazobenzothiazole compound represented by are obtained.

Maximum absorption wavelength of the obtained compound And the melting point was 174.5-176.0 ° C.

1.0 part of the compound represented by the formula (1) was atomized and dispersed in an aqueous medium together with 3.0 parts of a condensate of naphthalenesulfonic acid and formaldehyde. 10 parts of tetron jersey (polyester cloth, Teijin Ltd. product) was dipped in a dye bath containing 0.6 part of powder obtained by drying this dye dispersion, and pressure was applied 13
Staining was performed at 0 to 135 ° C for 60 minutes. The dyed product is then treated with 3 parts of caustic soda, 3 parts of hydrosulfite, 3 parts of betaine-type amphoteric surfactant and 3000 parts of water at 85 ° C.
After 10 minutes of reduction cleaning treatment, washed with water and dried,
A clear bluish red dyeing was obtained, which was excellent in light fastness, sublimation and wet fastness.

The obtained dyed product was subjected to softening / antistatic treatment according to the following method.

In the pad tank, Sumitex Softener LK-1 (Sumitomo Chemical Co., Ltd.'s softening agent) 10g / and Sumistat F
-1 (Antistatic agent manufactured by Sumitomo Chemical Co., Ltd.) was prepared as a pad solution having a composition of 5 g /, and the dyed product was dipped in this solution and then uniformly squeezed to a weight increase rate of 80%. Soak the dyed product in the liquid again, squeeze it in the same way, and then perform intermediate drying at 80 ° C for 2 minutes.
Then, heat setting was performed at 170 ° C. for 1 minute.

When the wash fastness of the thus obtained post-processed dyed product was measured, excellent results were obtained.

Example 2 The following formula (2) The compound represented by was synthesized according to the method described in Example 1. Maximum absorption wavelength of this compound The melting point was 177.1-180.3 ° C.

3.7 parts of ligninsulfonic acid was added to 1.3 parts of the compound represented by the above formula (2), and the mixture was atomized and dispersed, and 35 parts of warm water and 60 parts of a half emulsion paste having the following composition were mixed to prepare a printing agent.

O / W emulsion 300 parts Maypro gum NP 12% paste 694 parts Sodium chlorate 4 parts Tartaric acid 2 parts Total 1000 parts Tetron tropical (polyester cloth, manufactured by Teijin Ltd.) is printed with this printing paste and dried under normal pressure. Steaming was carried out at 170 ° C. for 7 minutes with a high-temperature steamer to fix, and reduction washing treatment, washing with water, drying, and softening / antistatic treatment were carried out in this order according to the method described in Example 1. The bright yellowish red dyed product thus obtained was excellent in light fastness, sublimation and wet fastness, and particularly excellent in fastness to washing.

Example 3 The following formula (3) The compound represented by was synthesized according to the method described in Example 1. Maximum absorption wavelength of this compound Met.

When a polyester cloth was dyed using this compound according to the method described in Example 1, a clear yellowish red dyed product having excellent wash fastness was obtained.

Example 4 The following formula (4) The compound represented by was synthesized according to the method described in Example 1. Maximum absorption wavelength of this compound Met.

When a polyester cloth was printed using this compound according to the method described in Example 2, a clear yellowish red dyeing product having excellent fastness to washing was obtained.

Example 5 According to the method described in Example 1, the compounds shown in Table 2 below were synthesized, and used to dye a polyester cloth,
A dyed product having the color tone shown in the table was obtained.

The fastness to washing of these dyed products was excellent.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kiyoho Hashimoto 3-1, 98 Kasugadechu, Konohana-ku, Osaka City, Osaka Prefecture Sumitomo Chemical Co., Ltd. (56) References JP-A-60-200170 (JP, A) JP-B-45-7712 (JP, B1) JP-B-60-29784 (JP, B2)

Claims (2)

[Claims] 1. The following general formula (I): (In the formula, X represents a hydrogen atom, a chlorine atom or a methyl group, and R represents an alkyl group having 1 to 4 carbon atoms.) A monoazobenzothiazole compound. 2. The following general formula (I) (Wherein X represents a hydrogen atom, a chlorine atom or a methyl group, and R represents an alkyl group having 1 to 4 carbon atoms), and a monoazobenzothiazole compound is used. A method of dyeing or printing.